Not applicable.
Not applicable.
Not applicable.
This invention is directed to emulsions and latexes prepared by forming a microemulsion of water, a surfactant, a hydride functional organosilicon oligomer or a mixture of such oligomers, and an alkenyl functional organosilicon oligomer or a mixture of such oligomers, and polymerizing the oligomer containing microemulsion until an emulsion or latex is formed containing polymer particles.
Silicone emulsion polymerization is a known technique for preparing silicone emulsions. The technique utilizes organosiloxane precursors, typically cyclosiloxanes or alkoxysilanes, which are substances capable of diffusion into or through water in their original form or when hydrolyzed. In silicone emulsion polymerization, siloxane polymers are formed from siloxane precursors and new emulsion particles are formed containing siloxane polymers formed during the polymerization process.
Confusion often is found in the literature as to what is meant by emulsion polymerization as it pertains to organosiloxane precursors. In this invention, emulsion polymerization means the process where new particles form that are characteristically smaller than the starting droplets of the organosiloxane precursor.
It should be noted that a key component enabling reactions to occur in silicone emulsion polymerization is a surface active catalyst, which has both the properties of a surfactant and a catalyst, described generally as a surfactant-catalyst. It is sometimes described as surfcat for the sake of brevity. Surfcats may be formed in situ in the emulsion polymerization process by ion exchange of a strong acid or base catalyst and an ionic surfactant that is the salt of a surface active strong acid or base, respectively. They can also be prepared beforehand by ion exchange of a strong acid or base catalyst and an ionic surfactant that is the salt of a surface active strong acid or base, respectively, in an aqueous solution.
The purpose of the surfcat is to catalyze the ionic polymerization of organosiloxane precursors to form particles containing siloxane polymers. Silicone emulsions that result from such a process, by design, contain ionic surfactants. The presence of ionic surfactants in silicone emulsions is unsatisfactory in applications where an electric charge on the particles is not desired. Therefore, a need exists for a silicone emulsion polymerization process that does not require a surfcat.
Hydrosilylation is a silicon-based reaction between silicon hydride and an unsaturated carbon bond that does not require an ionic catalyst.
While it""s not new to form emulsions and latexes by polymerizing mixtures containing water, surfactants, catalysts, hydride functional organosilicon oligomers, and alkenyl functional organosilicon oligomers, i.e., U.S. Pat. No. 3,900,617 (Aug. 19, 1975) and U.S. Pat. No. 4,248,751 (Feb. 3, 1981), it is not known to polymerize microemulsions containing low molecular weight, low viscosity organosilicon oligomers by the hydrosilylation reaction.
In instances where low molecular weight, low viscosity organosilicon monomers have been used, i.e., U.S. Pat. No. 6,013,682 (Jan. 11, 2000), the monomers contained no more than two reactive sites, and therefore network polymers could not be obtained, nor films of elastomeric or resinous materials upon removal of water.
The invention relates to a method for making emulsions or latexes that contain. polymer particles with a diameter greater than 0.02 micron (micrometer). The steps of the method generally involve the formation of a microemulsion that contains particles of one or more reactive siloxane oligomers having a diameter less than 0.02 micron (micrometer). The microemulsion is formed by combining water, at least one surfactant, a hydride functional organosilicon oligomer, and an alkenyl functional organosilicon oligomer. A catalyst is added to the microemulsion, and polymerization of the oligomers is initiated. Polymerization is allowed to continue until an emulsion or latex is formed containing polymer particles with a diameter greater than 0.02 micron (micrometer).
The oligomers each have a viscosity of 1-50 centistoke (mm2/s), and at least one oligomer contains more than two reactive sites.
While it is preferred to form the microemulsion in a single step by combining water, the surfactant, the hydride functional organosilicon oligomer, and the alkenyl functional organosilicon oligomer, and then adding the catalyst to the microemulsion; two separate microemulsions, each containing one of the oligomers, can be prepared and then combined, in which case the catalyst is included in the microemulsion containing the alkenyl functional organosilicon oligomer.
The emulsions and latexes resulting from these processes can be used in various applications such as hair fixative agents, release agents, and as thickening agents for low molecular weight silicone oils.
Cured films may be obtained by removing water from the resulting emulsion or latex. These films can be tailored to contain elastomeric or resinous polymers. Such films have utility as paper coatings, release coatings, and antifouling coatings, for example.
These and other features of the invention will become apparent from a consideration of the detailed description.
Not applicable.
Emulsions and latexes according to this invention are obtained from microemulsions of water, a surfactant, a hydride. functional organosilicon oligomer, and an alkenyl functional organosilicon oligomer, by polymerizing the microemulsion via hydrosilylation to form an emulsion or latex.
Hydrosilylation, as noted above, is a reaction involving addition of a silicon hydride to an unsaturated hydrocarbon to form a silicon-carbon bond. It is used commercially to synthesize organofunctional silicon monomers, to crosslink silicone polymers, and to connect a silicone to an organic polymer block to form a copolymer.
One example is hydrosilylation of an alpha-olefin with a methylhydrogen siloxane according to the general reaction
xe2x89xa1SiH+CH2xe2x95x90CHxe2x80x94Rxe2x86x92xe2x89xa1SiCH2CH2xe2x80x94R.
When used for crosslinking, such transition metal catalyzed hydrosilylation reactions typically involve reaction between a low molecular weight polysiloxane containing several Si-H groups and a high molecular weight polysiloxane containing at least two Si-vinyl groups, or vice versa.
Generally, equivalent molar amounts of the xe2x89xa1SiH groups and the unsaturated groups are employed in the process. It may be necessary, however, to use an excess of the reactant containing unsaturation to totally consume xe2x89xa1SiH in the siloxane product.
The maximum amount of transition metal catalyst employed is determined by economical considerations, and the minimum amount is determined by the type and purity of the reactants employed. Generally, very low concentrations of a platinum catalyst, such as 1xc3x9710xe2x88x9210 moles catalyst per equivalent of the reactant containing unsaturation, are used when the reactants are extremely pure. However, it is possible to use about 1xc3x9710xe2x88x928 moles catalyst per equivalent weight of reactant containing unsaturation, and even 1xc3x9710xe2x88x927 to 1xc3x9710xe2x88x923 moles of catalyst per equivalent weight of reactant containing unsaturation.
Reaction temperature can vary, and optimum temperatures depend upon the concentration of catalyst and the nature of the reactants. The reaction can be initiated at a temperature below room temperature, i.e., 0xc2x0 C., and is exothermic once it begins. For purposes of this invention, the temperature should be one at which both reactants are in a liquid state. The maximum temperature is determined by the range in which the microemulsion phase forms. It is preferred to operate the process such that the temperature is maintained above the lower critical temperature for microemulsion formation, and below the upper critical temperature for microemulsion formation. Ordinarily, it is best to keep the reaction temperature below about 100xc2x0 C. Best results with most reactants are obtained by initiating the reaction at about 50-80xc2x0 C. and maintaining the reaction within reasonable limits of this range. The exothermic nature of the reaction may require provisions for the removal of heat.
The optimum reaction time is variable depending upon the reactants, reaction temperature, and catalyst concentration. Ordinarily, there is no benefit in extending the contact time of reactants at the reaction temperature beyond 16 or 17 hours, but likewise there is usually no harm unless the resulting emulsion or latex stability is adversely affected. With many reactants, the reaction is complete in 30 minutes or less.
While the reaction can be carried out at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure, for the sake of simplicity, atmospheric pressure is generally preferred.
As noted, hydrosilylation requires a catalyst to effect the reaction between the SiH containing reactant and the reactant containing unsaturation. For purposes of this invention, liquid or liquid dispersible forms of the catalyst are preferred. Suitable catalysts include Group VIII transition metals, and typically platinum is the metal of choice. One example of a platinum metal catalyst which can be used is platinum in the form of a reaction product of chloroplatinic acid and an organosilicon compound containing terminal aliphatic unsaturation described in U.S. Pat. No. 3,419,593 (Dec. 31, 1968).
Another suitable catalyst is Karstedt""s catalyst described in U.S. Pat. No. 3,715,334 (Feb. 6, 1973) and U.S. Pat. No. 3,814,730 (Jun. 4, 1974). It is a platinum-vinylsiloxane substantially free of chemically combined halogen. Several other types of catalysts include deposited platinum and complexed platinum as described in U.S. Pat. No. 3,923,705 (Dec. 2, 1975).
Yet another suitable catalyst is a platinum-organosiloxane complex prepared by reacting platinous halide with an organosiloxane having 2-4 silicon bonded organic groups containing terminal olefinic unsaturation, in the presence of a polar organic liquid which is a partial solvent for the platinous halide, as described in U.S. Pat. No. 5,175,325 (Dec. 29, 1992).
Hydrosilylation can be initiated by catalysts other than Group VIII transition metals. For example, initiation can be induced by addition of a free radical initiator, or by photolysis, i.e., exposure to a light source such as ultraviolet light. Some examples of free radical initiators include peroxide type initiators, azo type initiators, and redox type initiators. Representative peroxide type initiators include diacyl peroxides, peroxyesters, dialkyl peroxides, and peroxydicarbonates, such as dibenzoyl peroxide, t-butyl peroxide, dicumyl peroxide, diisopropyl peroxy dicarbonate. An example of an azo initiator is 2,2-azobisisobutylonitrile. Examples of redox initiators are methylbutyl amine and dimethyl amine.
Monomers suitable for use according to the invention near and cyclic organosilicon oligomers represented by one following six formulas.
The first type of monomer is represented by: 
The second type of monomer is represented by: 
The third type of monomer is represented by: 
In the formulas, R1 represents an alkyl group containing 1-6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl. R1 can also be an aryl group such as phenyl. Preferably, R1 is methyl. R2 is the reactive group or site in the oligomeric molecule. R2 can be hydrogen or an alkenyl group. The value of a and b is 0-10, and the value of c is 1-10, provided the sum of b and c is 1-10. The value of d and e is 0-10, provided the sum of d and e is 3-10.
The alkenyl group is represented by the formula xe2x80x94(CH2)fCHxe2x95x90CH2 in which f can be zero or f can have a positive value of one to about six. Preferably, R2 is a vinyl group, an allyl group, or a hexenyl group.
These monomers should have a viscosity of 1-50 centistoke (mm2/s). The value of a, the value of the sum of b and c, and the value of the sum of d and e, should not exceed ten. This is for the reason that microemulsions can only be formed with low molecular weight, low viscosity organosilicon monomers.
In addition, at least one monomer used in the hydrosilylation reaction should have a functionality greater than two, i.e., it must contain more than two reactive sites in the molecule. This is necessary to form network polymers. Thus, by removing water from the composition, films of elastomeric or resinous materials can be provided.
Compositions particularly suitable for use herein are the hydride functional organosilicon oligomers 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and 1,1,3,3,5,5,7,7-octamethyltetrasiloxane; and the alkenyl functional oligomers 1,3-divinyltetramethyldisiloxane and 1,3,5,7-tetravinyl-1,3,5,7-tetramethyl cyclotetrasiloxane.
Other compositions suitable as hydride functional organosilicon oligomers are 3H,5H-octamethyltetrasiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, methylhydrocyclosiloxane, methyltris(dimethylsiloxy)silane, phenylhydrocyclosiloxane, phenyltris(dimethylsiloxy)silane, and 1,1,3,3-tetraisopropyldisiloxane.
Other compositions suitable as alkenyl functional organosilicon oligomers are
1,3-diallyltetrakis(trimethylsiloxy)disiloxane,
1,3-diallyltetramethyldisiloxane,
1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane,
1,5-divinyl-3,3-diphenyltetramethyltrisiloxane,
1,5-divinylhexamethyltrisiloxane,
1,5-divinyl-3-phenylpentamethyltrisiloxane,
divinyltetrakis(trimethylsiloxy)disiloxane,
divinyltetraphenyldisiloxane,
pentavinylpentamethylcyclopentasiloxane,
tetrakis(vinyldimethylsiloxy)silane,
1,1,3,3-tetravinyldimethyldisiloxane,
tris(vinyldimethylsiloxy)methylsilane,
tris(vinyldimethylsiloxy)phenylsilane,
1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane, and
1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane.
The first step in the process according to the invention is to form a microemulsion of a monomer or a mixture of monomers and water, using a surfactant system consisting of one or more surfactants and an optional cosurfactant. It should be understood that it is possible to form microemulsions of silicone monomers with a wide variety of surfactant systems, and so the surfactants described below are merely representative.
Thus, the surfactant can be a silicone polyether surfactant or it can be an organic surfactant.
The silicone polyether should be one which is generally water-soluble or water dispersible. It can have a rake type structure wherein the polyoxyethylene or polyoxyethylene-polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure.
Silicone polyethers suitable for use herein have the formula MD0xe2x88x921,000Dxe2x80x21xe2x88x92100 M, most preferably the formula MD0xe2x88x92500Dxe2x80x21xe2x88x9250M, where M represents monofunctional unit R3SiO1/2, D represents difunctional unit R2SiO2/2, and Dxe2x80x2 represents difunctional unit RRxe2x80x2SiO2/2. In these formulas, R is an alkyl group containing 1-6 carbon atoms or an aryl group, and Rxe2x80x2 is an oxyalkylene containing moiety. The Rxe2x80x2 groups may contain only oxyethylene (EO) units; a combination of oxyethylene (EO) and oxypropylene (PO) units; or a combination of oxyethylene (EO) units, oxypropylene (PO) units, and oxybutylene (BO) units. Preferred Rxe2x80x2 groups include oxyalkylene units in the ratio of EO3xe2x88x92100PO0xe2x88x92100, most preferably in the ratio EO3xe2x88x9230PO1xe2x88x9230.
Rxe2x80x2 moieties typically includes a divalent radical such as xe2x80x94CmH2mxe2x80x94 where m is 2-8 for connecting the oxyalkylene portion of Rxe2x80x2 to the siloxane backbone. Such moieties also contain a terminating radical for the oxyalkylene portion of Rxe2x80x2 such as hydrogen, hydroxyl, or an alkyl, aryl, alkoxy, or acetoxy group.
Silicone polyethers useful herein can also be of a type having the formula Mxe2x80x2D10xe2x88x921,000Dxe2x80x20xe2x88x92100Mxe2x80x2, most preferably the formula Mxe2x80x2D10xe2x88x92500Dxe2x80x20xe2x88x9250Mxe2x80x2, wherein Mxe2x80x2 represents monofunctional unit R2Rxe2x80x2SiO1/2, D represents difunctional unit R2SiO2/2, and Dxe2x80x2 represents difunctional unit RRxe2x80x2SiO2/2. In these formulas, R can be an alkyl group containing 1-6 carbon atoms or an aryl group, and again Rxe2x80x2 represents an oxyalkylene containing moiety. As noted previously, Rxe2x80x2 groups typically contain only oxyethylene (EO) units or combinations of oxyethylene (EO) and oxypropylene (PO) units. Such Rxe2x80x2 groups include these oxyalkylene units in the ratio EO3xe2x88x92100PO0xe2x88x92100, most preferably EO3xe2x88x9230PO1xe2x88x9230.
As also noted previously, Rxe2x80x2 moieties typically include a divalent radical xe2x80x94CmH2mxe2x80x94 where m is 2-8 for connecting the oxyalkylene portions of Rxe2x80x2 to the siloxane backbone. In addition, the moiety Rxe2x80x2 contains a terminating radical for oxyalkylene portions of Rxe2x80x2 such as hydrogen, hydroxyl, an alkyl, aryl, alkoxy, or acetoxy group.
In addition, silicone polyethers useful herein can be of a type having the formula MD0xe2x88x921,000Dxe2x80x20xe2x88x92100Dxe2x80x31xe2x88x921,00M wherein Dxe2x80x3 represents difunctional unit RRxe2x80x3SiO2/2, and Rxe2x80x3 is an alkyl group containing 1-40 carbon atoms. M, D, Dxe2x80x2, and R, are the same as defined above.
These silicone polyethers are known in the art and are commercially available from Dow Corning Corporation, Midland, Michigan. One silicone polyether especially preferred for use herein is the short chain linear silicone polyether 1,1,1,3,5,5,5-heptamethyl-3-[propyl(polyEO7)hydroxy)]trisiloxane.
While such silicone polyethers are capable of functioning as the sole emulsifying agent, other types of organic surfactants can be used, either in place of or in combination with the silicone polyether surfactant, if desired.
Such other surfactants can be nonionic, cationic, anionic, amphoteric (zwitterionic), or mixtures of such surfactants. Nonionic surfactants most preferred are alcohol ethoxylates R2xe2x80x94(OCH2CH2)xOH, most particularly fatty alcohol ethoxylates. Fatty alcohol ethoxylates typically contain the characteristic group xe2x80x94(OCH2CH2)xOH which is attached to fatty hydrocarbon residue R2 which contains about eight to about twenty carbon atoms, such as lauryl (C12), cetyl (C16) and stearyl (C18). While the value of x may range from 1 to about 100, its value is typically in the range of 2 to 40.
Some examples of suitable nonionic surfactants are polyoxyethylene (4) lauryl ether, polyoxyethylene (5) lauryl ether, polyoxyethylene (23) lauryl ether, polyoxyethylene (2) cetyl ether, polyoxyethylene (10) cetyl ether, polyoxyethylene (20) cetyl ether, polyoxyethylene (2) stearyl ether, polyoxyethylene (10) stearyl ether, polyoxyethylene (20) stearyl ether, polyoxyethylene (21) stearyl ether, polyoxyethylene (100) stearyl ether, polyoxyethylene (2) oleyl ether, and polyoxyethylene (10) oleyl ether. These and other fatty alcohol ethoxylates are commercially available under names such as ALFONIC(copyright), ARLACEL, BRIJ, GENAPOL(copyright), LUTENSOL, NEODOL(copyright), RENEX, SOFTANOL, SURFONIC(copyright), TERGITOL(copyright), TRYCOL, and VOLPO.
Cationic surfactants useful in the invention include compounds having quaternary ammonium hydrophilic moieties in the molecule which are positively charged, such as quaternary ammonium salts represented by R3R4R5R6N+Xxe2x88x92 where R3 to R6 are alkyl groups containing 1-30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soy; and X is halogen such as chlorine or bromine, or X can be a methosulfate group. Most preferred are (i) dialkyldimethyl ammonium salts represented by R7R8N+(CH3)2Xxe2x88x92, where R7 and R8 are alkyl groups containing 12-30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soy; and X is halogen or a methosulfate group; or (ii) monoalkyltrimethyl ammonium salts represented by R9N+(CH3)3Xxe2x88x92 where R9 is an alkyl group containing 12-30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soy; and X is halogen or a methosulfate group.
Representative quaternary ammonium salts are dodecyltrimethyl ammonium bromide (DTAB), dodecyltrimethyl ammonium chloride, tetradecyltrimethyl ammonium bromide, tetradecyltrimethyl ammonium chloride, hexadecyltrimethyl ammonium bromide, hexadecyltrimethyl ammonium chloride, didodecyldimethyl ammonium bromide, dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, didocosyldimethyl ammonium chloride, dicoconutdimethyl ammonium chloride, ditallowdimethyl ammonium chloride, and ditallowdimethyl ammonium bromide. These and other quaternary ammonium salts are commercially available under names such as ADOGEN, ARQUAD, SERVAMINE, TOMAH, and VARIQUAT.
Examples of anionic surfactants include sulfonic acids and their salt derivatives such as dodecylbenzene sulfonic acid (DBSA); alkali metal sulfosuccinates; sulfonated glyceryl esters of fatty acids such as sulfonated monoglycerides of coconut oil acids; salts of sulfonated monovalent alcohol esters such as sodium oleyl isothionate; amides of amino sulfonic acids such as the sodium salt of oleyl methyl tauride; sulfonated products of fatty acid nitriles such as palmitonitrile sulfonate; sulfonated aromatic hydrocarbons such as sodium alpha-naphthalene monosulfonate; condensation products of naphthalene sulfonic acids with formaldehyde; sodium octahydro anthracene sulfonate; alkali metal alkyl sulfates such as sodium lauryl (dodecyl) sulfate (SDS); ether sulfates having alkyl groups of eight or more carbon atoms; and alkylaryl sulfonates having one or more alkyl groups of eight or more carbon atoms.
Commercial anionic surfactants useful herein include triethanolamine linear alkyl sulfonate sold under the name BIO-SOFT N-300 by the Stepan Company, Northfield, Ill.; sulfates sold under the name POLYSTEP by the Stepan Company; and sodium n-hexadecyl diphenyloxide disulfonate sold under the name DOWFAX 8390 by The Dow Chemical Company, Midland, Mich.
Surfactants classified as amphoteric or zwitterionic include cocoamphocarboxy glycinate, cocoamphocarboxy propionate, cocobetaine, N-cocamidopropyldimethyl glycine, and N-lauryl-N-carboxymethyl-N-(2-hydroxyethyl)ethylene diamine. Other suitable amphoteric surfactants include the quaternary cycloimidates, betaines, and sultaines.
The betaines have the structure R11R12R13N+(CH2)nCOOxe2x88x92 wherein R11 is an alkyl group having about twelve to eighteen carbon atoms or a mixture thereof, R12 and R13 are independently lower alkyl groups having one to three carbon atoms, and n is an integer from one to four. Specific betaines are
xcex1-(tetradecyldimethylammonio)acetate,
xcex2-(hexadecyldiethylammonio)propionate, and
xcex3-(dodecyldimethylammonio)butyrate.
The sultaines have the structure R11R12R13N+(CH2)nSO3xe2x88x92 where R11, R12, R13 and n are defined above. Useful sultaines include 3-(dodecyldimethylammonio)-propane-1-sulfonate and 3-(tetradecyldimethylammonio)ethane-1-sulfonate.
Representative amphoteric surfactants are products sold under the names MIRATAINE(copyright) by Rhone-Poulenc Incorporated, Cranberry, N.J.; and TEGO BETAINE by Goldschmidt Chemical Corporation, Hopewell, Virginia. Imidazoline and imidazoline derivatives sold under the name MIRANOL(copyright) by Rhone-Poulenc Incorporated, Cranberry, N.J. may also be employed.
Since emulsions are susceptible to microbiological contamination, a preservative can be used as an optional component in the emulsion. Representative of some compounds which can be used include formaldehyde, salicylic acid, phenoxyethanol, DMDM hydantoin, i.e., 1,3-dimethylol-5,5-dimethyl hydantoin, 5-bromo-5-nitro-1,3-dioxane, methyl paraben, propyl paraben, sorbic acid, imidazolidinyl urea sold under the name GERMALL(copyright) II by Sutton Laboratories, Chatham, N.J. sodium benzoate, 5-chloro-2-methyl-4-isothiazolin-3-one sold under the name KATHON CG by Rohm and Haas Company, Philadelphia, Pa., and iodopropynl butyl carbamate sold under the name GLYCACIL(copyright) L by Lonza Incorporated, Fair Lawn, N.J.
Addition of a cosurfactant such as a short chain alcohol may also be necessary to form a microemulsion phase with many organic and siloxane surfactants. Representative examples of such cosurfactants are 1-butanol, 1-pentanol, 1-decanol, 1-hexadecanol, ethylene glycol, propylene glycol, trimethylene glycol, and glycerol.
A freeze/thaw stabilizer can be used as an optional component of the emulsion. Representative compounds include ethylene glycol, propylene glycol, glycerol, trimethylene glycol, and polyoxyethylene ether alcohols such as products sold under the name RENEX 30 by ICI Surfactants, Wilmington, Del.
Salts other than salts mentioned above as surfactants can be used as an optional component. These salts can be inorganic salts or organic salts such as compositions generally referred to as an electrolyte. Their inclusion in the composition is primarily for the purpose of expanding the region in which the microemulsion phase forms for compositions that include ionic surfactants.
Some examples of inorganic salts which can be used are calcium chloride, magnesium sulfate, magnesium chloride, sodium sulfate, sodium thiosulfate, sodium chloride, sodium phosphate, ammonium chloride, ammonium carbonate, iron sulfate, aluminum sulfate, aluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, aluminum dichlorohydrate, aluminum zirconium tetrachorohydrex glycine, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate, and aluminum zirconium octachlorohydrate.
Suitable organic salts include sodium aluminum lactate, sodium acetate, sodium dehydroacetate, sodium butoxy ethoxy acetate, sodium caprylate, sodium citrate, sodium lactate, sodium dihydroxy glycinate, sodium gluconate, sodium glutamate, sodium hydroxymethane sulfonate, sodium oxalate, sodium phenate, sodium propionate, sodium saccharin, sodium salicylate, sodium sarcosinate, sodium toluene sulfonate, magnesium aspartate, calcium propionate, calcium saccharin, calcium d-saccharate, calcium thioglycolate, aluminum caprylate, aluminum citrate, aluminum diacetate, aluminum glycinate, aluminum lactate, aluminum methionate, aluminum phenosulfonate, potassium aspartate, potassium biphthalate, potassium bitartrate, potassium glycosulfate, potassium sorbate, potassium thioglycolate, potassium toluene sulfonate, and magnesium lactate.
The oil component of the microemulsion consists of the organosilicon oligomers in an amount of about 0.1-50 percent by weight based on the total weight of the microemulsion. The surfactants are used in amounts of about 1-30 percent by weight including any cosurfactants which may be present, based on the total weight of the microemulsion. Water constitutes about 20-98.9 percent by weight based on the total weight of the microemulsion. The transition metal catalyst or free radical initiator constitutes about 1-5,000 parts per million by weight based on the weight of the oil phase. The amount of optional components can be from zero to about ten percent by weight based on the total weight of the microemulsion.
Microemulsions, emulsions, latexes, and suspensions according to the invention can be prepared without application of high shear, and do not require the use of special equipment for producing high shear, such as propeller mixers, turbine-type mixers, Brookfield counter-rotating mixers, or homogenizing mixers. In many cases, simple handshaking is sufficient, or a simple laboratory stirring device will be adequate.